Mineral oil composition



I MINERAL OHIL CGOSITKGN Orland M. Reifi, Woodbury, N. 1., and Ferdinand P. tto,.Philadelphia, Pa, assignors to Socony- Vacuum Oil Company, Incorporated, New York, N. Y., a corporation oi New York No Drawing. Application September 12, 1939, Serial No. 294,482

32 Claims (Cl. 87-9) This invention has to do in a general way with In the lubrication of internal combustion enmineral oil compositions and is more particularly gines, particularly those operating with high related to mineral oil compositions of the lubricylinder pressures, there is a decided tendency for Cant type 1 Which an agent h been added for the ordinary lubricating oil fractions to form.

5 the Pu p Of improving the Oil in certain under such conditions of use, carbonaceous de- 5 spects. It is the object of this invention to proposits which cause t piston rings t b e vide a novel class of mineral oil addition agents stuck in their siots and which fill t l t i th which will impro One more important P P- oil ring or rings, thus materially reducing the erties of a mineral oil fraction. It is a further emcjency of the engine. Ingredients have there.

Object to provide improved humeral on fore been'developed which when added to the oil 10' Positions Containing Such improving a n will reduce the natural tendency of the oil to form It is Well k own to those familial with the art deposits which interfere with the function of the that mineral oil fractions refined for their various piston rings uses are in a Of themselves usually deficient Aside from the corrosive action which attends in one or more l'espects, so that Pheir practical the formation of acidic products of oxidation in 15 utility is limited even in the particular field for miherai oi] fra tions of t iuhricani; range 11;

which they e been n example, has been discovered that certain types of recently mineral oil fractions refined for use as lubricants developed hard metal alloy bearing metals, such have a tendency to oxidize under conditions of as cadmium si1ver alloy bearings are tt k use with the formation of sludge or acidic 0xida-' by ingredients. in t v types of oils, m

tion products; also the lighter fractions such isriy oiis of high viscosity index obtained by as gasoline and kerosene tend to oxidize with the various t s of 1 This chm)- formation of color bodies, gum, etc. In order to i action on alloys of th above type h led to prevent the formation these Products and the development of corrosion inhibitors which thereby extend the useful life of the oil fraction, may he used in soiventqefined oils t t t such it is co o p a to blend i Such Oil frac' bearing metals against this corrosive action.

tions an additive ingredient which will have the r In the lighter mineral oil fractions, such as effect of inhibiting oxidation, such ingredients those used for fueipurposes, particularly i being generally known to the trade asoxidationtemai ombustion engines, it has been found that inhibitors or sludge inhibitors, gum inhibitors, the combustion characteristics of the fu l. may 30 etc. be controlled and improved by adding minor pro- It is also the practice to add other ingredients portions f various improving agents t t to mineral oil fractions for the purpose of im- The various ingredient which have been proving the oiliness characteristics and wearveloped for use in mineral i fra tion t reducing action of such mineral oils when they prove such fractions in the various respects enuare used as lubricants, particularly when the memted a v are largely specific t th i particoils are used for the purpose of lubricating metal uiar applications, and has therefore b t surfaces which are engaged under ex r m ly high practice to add a separate ingredient for each of Pressures and at high rubbing Speedsthe improvements which is to be eflected.

40 Other ingredients have been developed for the is a primary object of, th present ihvem 40 p p of depressing the P Point of mineral tion to provide mineral oil-improving agents oil fractions which have been refined. for use as which are muitiiunctiohai in t t a single lubricants, such refinement leaving a certain dieht may he added to the oil t efiect, i r vamount of wax in the oil, which Without the merit in one more of t various properties added ingredient would tend to cryst at enumerated above. More specifically, our inventemperatures which render the oil impracticable tion contempiates as oii improving agents t for .use under low temperature conditions. Adi ibl m tal salts of alkyl-substituted hyditive agents have 8180 been developed for droxyaromatic-aliphatic carboxylic acids in proving the viscosity index of lubricating oil which the hydroxyl hydrogen and the'carboxyl fractions. hydrogen are substituted with metal. We have ill I cific object the-provision of a viscous mineral oil discovered that metal salts of the general class above referred to'may be added in small quantities to mineral oil fractions to form mineral oil compositions or blends superior to the unblended fractions in one or moreimportant respects, and the present invention, therefore, is broadly 'directed to a mineral oil composition containing a compound falling into the general class referred,

' Our invention has as a further and more spefraction which has been improved in one or more of the foregoing recited respects by having incorporated therein a minor proportion of an 011-,

miscible metal salt of an alkylated hydroxyaromafia-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carbonyl hydrogen, are

r'eplacedwith anorg'anic acidgroup such as a monoor po'lybasic aliphatic or cyclo aliphatic acid, group in which the hydroxyl hydrogen and the carbonyl hydrogen are substituted with their equivalentweightof metal; Compounds or compositions of this type are thereforecharacterized by the presence of an aromatic nucleus in which atleast one nuclear hydrogen has been replaced,

' with a metaloxy (OMlsubstituent and in which another nuclear hydrogen atom is replaced with an aliphatic acid salt residue (Z.CO'OM).

I (The terms aliphatic carboxylic' acid and alkyl carboxylic acid as used herein are inclusive of aliphatic and cyclo aliphatic acids.) .This characterizing group may be represented by the formula: c 1

r. I rwmlaoooor) in which T represents an aromatic nucleus;

(OM) represents at least one hydroxyl group attached to T, the hydrogen thereof being replaced by a metal M; and (ZCOOM) represents at least one aliphatic or cycle-aliphatic acid residue attached to the nucleus T, in which Z represents the aliphatic or cycle-aliphatic radical attached to T and COOM' is at least one carboxyl group attached to Z, the hydrogen thereof being replaced with its equivalent weight of a metal M.

The metal salts of hydroxyaromatic-aliphatic acids of the type corresponding to the group represented by the above formula which are otherwise unsubstituted are not in general miscible with mineral oil, particularly where the alkyl acid residue is derived from a low molecular weight acid. When the residue Z.COOM' is derived from a high molecular weight acid such as stearic acid, the salts may, with some difficulty, be blended with oil, but tend to cause gelation, which is undesirable. It is therefore important that the improving agents containing the above characterizing group have additional nuclear hydrogen replaced with substituents of an oil-solubilizing nature. In other words, it is important that the aryl nucleus T carry a substituent or substituents which will render the composition as a whole miscible with mineral oil fractions andwill prevent gel formation therein. By the terms oilmiscible or oil-soluble as they are used her'e-.

in we have reference to that property of remaining uniformly dispersed in the mineral oil fraction, either as a true solution or as a colloidal suspension Without gelation during normal conditions of handling and use.

this

The improving agents. contemplated by this alkyl substituents directly or indirectly substiinvention are characterized by the presence of tuted in the aryl nucleus T, and theimproving agents preferred for use in viscous mineral oils are further characterized by the presence'of alkyl or aliphatic substituents in the aryl nucleus T which will give other properties to the composition as a whole in addition tooil-miscibility. We

have found,for example, that where this aryl I nucleus is substituted with one or more aliphatic groups corresponding to certain aliphatic hydrocarbon compounds of relatively high molecular weight (such as aliphatic groups having at least twentycarbon atomsherein referred to as heavy allryl groups), a compound or composition can be obtained which will effect marked improve I bilizing substituent such as ,a predominantly aliphatic material, such substituent comprising a sufficient proportion of the composition a oil fractions under normal conditions of handling and use. As a further generalization it may be said that at least one point on the aromatic nucleus T, and preferably two'or more points on suchnucleus, is substituted with aliphatic hydro carbon radicals or groups, suchaliphatic radicals or groups preferably being high molecular weight aliphatic derivatives or heavy alkyl groups.

' The simplest type of compound satisfying the above requisites may be represented by the formula:

ii. R(T(OM) (Z.COOM) in which R represents at least one aliphatic hydrocarbon radical or group, such group or groups preferably corresponding to relatively high molecular weight aliphatic hydrocarbons and being attached to a monoor polycyclic aromatic nucleus T, and in which (OM) and (ZCOOIVY) are as indicated above.

In addition to the aliphatic or alkyl substituent R, the compounds or compositions contemplated herein as mineral oil-improving agents may have additional nuclear hydrogen of the aryl nucleus T replaced with other substituents which may or may not have a solubilizing effect upon the composition as a Whole. Such a compound in its simplest form may be represented by the formula:

III. R(T(OM) (COOM')Y) in which R, T, (OM) and (Z.COOM) have the compound wherein R contains at least twenty carbon atoms, Y may also include alkyl radicals of less than twenty carbon atoms. Compounds of the above general formula-type having mono-,

merit in the'viscosity index and the pour point,

' this invention are metal salts of hydroxyai'o matic aliphatic vcarboi zylic characterizing group T(OM)(Z.COOM) '30 Whole to render the same miscible with mineral I di and tricyclic nuclei are illustrated by the following specific formulae:

. R OM n Z.COOM' I I R R but for purposes of description and illustration herein the former type of formula will be used, with the understanding that M and M may represent different metals or the same monoor poly-valent metals and withvthe further understanding'that when M and M represent the same polyvalent metal, a single atom of such metal may replace both the hydroxyl and the carboxyl hydrogens to form a Chelate ring.

Relative to this alkyl carboxylate substituent we have found that it is advantageous to have the carboxylate group in a hydrocarbon substituent or side chain attached to the characterizing aromatic nucleus for the-reason that compounds of this type are more stable against the formation of emulsions than are compounds of the type in which the carboxyl group is directly attached to the aromatic nucleus. Furthermore,

aromatic-aliphatic carboxylate compounds 'of the type contemplated herein are characterized by the fact that the metal substituent is less susceptible to removal by water-washing, which per-' mits more complete purification of the compound and removalof reaction products, such as inorganic salts, which might be found objectionable in mineral oil compositions compounded for certain uses.-

-In the foregoing examples it will be observed that the aliphatic or alkyl substituent is a monovalent aliphatic hydrocarbon group, but, as will appear from the hereinafter-described synthesis of our oil-improving agent, part or all of the aliphatic hydrocarbon material may be comprised of polyvalent aliphatic hydrocarbon radicals or groups in which the several valence bonds are attached to separate aromatic nuclear groups 'I'.

Compounds of this type are included under the following general formula representation:

.IV. R"(T(OM) (COOM') Yb) n in which T, (OM) and (Z.COOM') have the same significance indicated above; R represents at least one aliphatic or alkyl radical or group, such alkyl group or groups being attached by one valence bond only to at leastone aromatic nucleus T, 2; representing the Valence of the aliphatic radical R", which may be one to four; Yb represents a monovalent element or group selected from the class identified abovein connection with Y; 12 represents the number of Ybs and is equal to zero or a whole n.umber corresponding to the valence'bo-nds on the nucleus T not satisfied with R", (OM) and (Z.COO1VI'); and n represents a whole number from one to four and indicates the total number of groups (T(OM)(COOM')Yb) present in the molecule represented by the formula which are attached to the-aliphatic group or groups represented by R through the valence bonds 1).

Inthe foregoing general formula representation IV it will be seen that the compounds represented thereby include those materials in which all of the aliphatic substituent is monovalent (:1 and 11:1) or in which all of the aliphatic substituent is polyvalent (22 and n being equal to 2, 3 or 4) or since R is defined as being at least one aliphatic radical or group and may therefore include several such groups, it will be seen that this general Formula IV is inclusive of compounds having aliphatic groups or radicals of different valences (from 1 to 4) in the same molecule.

- Also, it will be observed that since n may be any whole number from 1 to 4, the number of aroe.

matic nuclei T in the molecule may likewise vary from 1 to 4. It will be seen, therefore, that the relationship between n and v in Formula IV, in its broadest aspect is such that when n is equal to l, 'v is equal to 1; and when n is greater than 1, the valence v of at least one of the R's is equal to n (in order'to tie the several nuclei or TS together), the valence of any remaining Rs being any whole number equal to or less than 11..

As stated above and as willappear more fully later on from the description of their synthesis,

these materials represented 'by general Formula IV may contain both monovaleut and polyvalent aliphatic substituents. Both the polyvalent aliphatic substituent and the monovalent substituent, if both are present, may be introduced in the nucleus as part of an alkylation reaction, or all or part of the monovalentaliphatic substituent may be present in the nucleus of a hydroxyaromatic starting material as low molecular weight aliphatic groups, such as methyl, ethyl,

,Which all of the alkyl substituent is comprised of heavy alkyl groups, which compounds are highly elfect ive pour point depressants in addition to being V. I. improvers and inhibitors of oxidation.

Compounds of the general type last-described above, which include polyvalent-substituted aliphatic substituents and may also include both the monovalent and the polyvalent substituents, are included under the subgeneric formula representation:

in which T, (OM) and (ZIJOOM!) have the same significance as indicated above; R represents at least one polyvalent aliphatic radical or group having a valence v of 2, 3 or 4 and preferably containing at least twenty carbon atoms; Yb indicates the same group of substituents as described above for Ye; R0 represents monovalent aliphatic radicals or groups and may include radicals containing less than twenty carbon atoms; b represents the number of Yws and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied with R, (OM), (Z.COOM) and Re; 0 indicates the numberof Rcs and is equal to zero or a whole number corresponding to the valence bonds on the nucleus T not satisfied with RF, (OM), (Z.COOM') and Yb; and n represents a whole number from two to four and indicates the total number of the groups (T(OM) (Z.COOM)YbRc) present in the molecule represented by the formula which are attached to the aliphatic group or groups represented by R"' through the valences o.

In the above general Formulae IV and V it will be understood that since R" and R are aliphatic hydrocarbon radicals of the chain type and are each attached by one valence bond only to each corresponding aromatic nucleus, the valence v or v" of such radical or radicals is of necessity never greater than the number 11, which indicates the number of aromatic nuclei in the molecule and in Formula IV is always equal to 1 when n equals 1. Otherwise an R or an R having a valence greater than the number (n or n) of aromatic nuclei would either have some of its valence bonds unsatisfied or else would form a condensed ring or rings by attachment at two or more points to one, and the same aromatic nucleus. Such latter compounds, as already indicated from the definition of R" or R are not considered as characterizing the product of the present invention although probably formed in some instances in minor amounts as unobjectionable by-products by certain of the methods of preparation herein disclosed.

A simple type of compound coming under general Formula IV in which 1) and n is each to 1 and in which there is only one oil-solubilizing aliphatic group R may be illustrated by the following formula showing T for purposes of illustration as a monocyclic nucleus:

In the above formula the chain represents the oil-solubilizing alkyl substituent (R and Ya OM and Z.COOM' have the same significance as has been heretofore given to these groups.

Since group R". has been defined as at least one," it will be apparent that there may be more than one heavy alkyl 'substituent attached to the nucleus T. Such a compound, where v and n are each 1 and in which there are two such I monovalent R groups, may be represented by the following formula:

B. OM Z.COOM

H H H H Ho------o -o------on H H H H in which the chains and the substituent characacters have the same significance defined above.

Compounds of the type satisfying the general Formula IV and the subgeneric Formula V in which R' (or RF) is polyvalent and v (or e) and n (or n) are more than 1 and in which there is only one such polyvalent R group may be illustrated by the following formula, in which the aryl nucleus T is again indicated for illustration as being monocyclic:

H l V H no-- -0 -o --c GH ll H n H In the above Formula C, Re is a monovalent alkyl group as defined above under Formula V.

Under this same type of compound indicated by Formula C there may also be more than one polyvalent R group (represented by the chain), such a compound in which there are, for example, two polyvalent R groups being illustrated by the following formula, in which the characterizing groups have the same significance described above under Formula C.

n n n 11 n no --o --o --c --on n 11 2.00011 Z.COOM Z.COOM Y,, OM Y -jOM yi,mom

R, at a, n 11 no --c --o --on H n 11 n n Such a compound may be typified by the following formula in which the symbols have the same significances as in Formula C:

V H y H no --o --c --on it n H H groups which can be attached to a single aromatic nucleus will vary as the nucleus is monoor polycyclic and also as the nucleus is otherwise substituted. It will also be apparent that the nuclear" hydrogen atoms available for replacement on several interrelated nuclei may all be substituted with polyvalent aliphatic substituents.

It will be understood that the oil-improving agents used in the mineral oil compositions contemplated by this invention may be pure compounds satisfying the general Formula IV described above with any one of the various monoand poly-cyclic aromatic nuclei as T and the various substituents R (or R and Y) described. However, in manufacturing the preferred oilimproving product of the present invention by the preferred method of procedure, as will appear more fully later on, the final oil-improving product obtained is normally or usually a mixture of different compounds corresponding to different values of n and v and to different numbers of aliphatic groups R".

As has been emphasized hereinabove, it is important that the oil-improving agents as represented by general Formulae IV and V have nuclear hydrogen in the aromatic nucleus T substituted with predominantly aliphatic material which comprises a sufficient proportion of the composition as a whole to render the same miscible with the mineral oil fraction in which the improving agent is used under normal conditions of handling and use. It appears from the results of our research that there is a more or less critical range in the degree of alkylation of these improving agents below which the product or agent willnot satisfy the requirements for oil-miscibility or oil-miscibility and multifunctional activity. Expressing' this in another way, it appears that the hydroxyaromatic constituent of the alkylated hydroxyaromatic compound from which the alkylated metal-oxyaromatic-aliphatic carboxylate metal salt is derived should not exceed a certain percentage of such alkylated hydroxyaromatic composition as a whole.- This critical range of alkylation may be roughly expressed as the ratio by weight of (T(OH))11 to R (T(OH))n.

The degreeof alkylation and the critical ranges within which operative and preferred compounds can be obtained may also be expressed as the number of carbon atoms contained in the aliphatic substituents for each aryl nucleus in a given molecule or molecular structure.

The critical range in the degree of alkylation of the aryl nucleus in the improving agents contemplated herein may vary with: (a) the mineral oil fraction in which the improving agent is to be used; (1) the and nucleus T (monoor polycyclic); (c) the hydroxyl content of the aryl nucleus from which the final product is obtained (monoor po y-hydric); (d) the character of aliphatic material comprising the substituent (straight or branched chain); (c) monoor poly= areaeve substitution 0'1 the aryl nucleus; 0) other sub stituents on the nucleus T, which may be of positive or negative or of neutral solubilizing activity; and (g) the character of the aliphatic group in the aliphatic acid residue (Z) carrying the COOM' group or groups.

In general it may be said that a polycyclic nucleus appears to require a higher degree of alkylation than a monocyclic nucleus; that a polyhydric nucleus requires a higher degree of alkylation than a monohydric nucleus; and that branched chain aliphatic substituents have a somewhat greater solubilizing action than straight chain solubilizing substituents. Also, the condensation product containing a high molecular weight aliphatic acid residue such as an hydroxy-aryl stearic acid does not require for mere oil-solubility as extensive alkylation as the derivative containing a low molecular weight aliphatic acid group such, for example, as acetic acid.

In view of the foregoing variables it would be impracticable and probably misleading to" attempt to give an expression and figure which would indicate accurately the proper ratio of hydroxyaromatic constituent to the alkylated hydroxyaromatic constituent which would ex-' press a degree of aliphatic substitution satisfying all cases taking these variables into account. As

a guide for preparing these improving agents, however, our research indicates that fora product having pour-depressing and V. I.-improving properties in addition to other valuable properties the ratio of (T(OM) (Z-COOM)n to R T(OM) (COOM) )1: expressed as:

should not be greater thanabout .15 when the weight of the hydroxyaromatic nucleus or component (T(OH))n is expressed in terms of its chemically equivalent weight of phenol (CsHaOI-I) However, for mere oil-solubility with inhibition of oxidation we have found that this ratio may be raised. For example, salts of the type contemplated herein which satisfy the requisites of oil-miscibility without gelation can be prepared from phenol-stearic acid having alkyl substituents as low as amyl or tertiary butyl. In general it may be said that in the preferred improving agents contemplated herein the ratio by weight of the hydroxyaromatic component in the product to the corresponding alkylated hydroxyaromatic nucleus. or component therein should not be greater than about 15 parts by weight of the former to about parts by weight of the latter, or about 15 per cent, when the weight of the hydroxyaromatic nucleus or component is expressed in terms of its chemically equivalent weight of phenol. It will be observed that the ratio as represented by the Formula VI does not take into account any other substituent in the nucleus than the aliphatic substituents and the hydroxyl group or groups; but since the aliphatic substituent is primarily relied upon in the agents contemplated herein as the solubilizing substituent, it is believed that the foregoing expression and limits will serve as a working guide for the preparation of oil-soluble materials and the preferred multifunctional materials.

As stated above, the degree of alkylation may also be expressed by the number of carbon atoms contained in the aliphatic substituent for a given hydroxyaromatic nucleus T. As a general guide here it may be said that the aliphatic substituents represented by R in the above general Formula IV should, for the preferred multifunctional materials contemplated herein, contain a total of at least twenty-five carbon atoms for each arcmatic nucleus T.

The ratio of per cent, which we may term the phenolic ratio, represents what we consider a maximum figure for the preferred products contemplated herein, and in general it will be found that for these preferred multifunctional products this figure will be lower, the actual ratio, of course, being dependent upon the variable factors enumerated above.

A further general guide for the synthesis of the preferred improving agents for viscous oils is to alkylate the aromatic nucleus so that it is poly-substituted with aliphatic hydrocarbon radicals or groups preferably of relatively high molecular weight: that is, groups having at least twenty carbon atoms,

As has been previously indicated, it is one of the primary objects of the invention to provide an oil-improving agent which will have multifunctional improving activity in a mineral oil. Our research indicates that compounds satisfying the requisites of general Formula IV above may be blended in minor proportions with mineral oil fractions, particularly of the viscous or lubricating oil type, to effect marked improvement in several important properties. The improvement effected may be varied somewhat with the aliphatic substituent, petroleum wax and aliphatic compounds of similar characteristics such "as ester wax,'for example, giving products which effect a marked improvement in viscosity index, pour point, inhibition of oxidation, retardation of lacquer formation or ring-sticking, etc. The effectiveness may also be varied with other substituents in the aryl nucleus, as has been previously indicated. Low molecular weight alkyl groups or halogen, as nuclear substituents, tend to modify the properties of the compounds by reducing the pour point-depressing action without disturbing their effectiveness as V. I.- improvers and antioxidants. The properties of the agents may also be varied with the character of the metal substituent in the hydroxyl and the carboxyl groups. In general it appears that the oil-miscible heavy alkyl-substituted salt of any metal satisfying the requisites of Formula IV above will provide a multifunctional oil-improving agent in that they improve the V. I. and. function as inhibitors. Certain of the metals, such, for example, as copper, lead, and zinc, may serve to increase the load-carrying capacity of lubricating oils.

The general procedure followed in synthesizing the oil-improving agents contemplated herein involves substituting a nuclear hydrogen atom on an allq lated hydroxyaromatic compound with an aliphatic or cyclo-aliphatic carbomlic acid group and then substituting the hydroxyl hydrogen and the carboxyl hydrogen with metal. In the event one of the preferred. multifunctional products is desired, the alkylated hydroxya omatic compound is obtained by condensing a substituted or unsubstituted monoor polycyclic hydroxyaromatic compound with a high molecular weight aliphatic compound containing at least twenty carbon atoms. c

The alkylation procedure last-mentioned above may be carried out in various ways, as by the use of a halogenated high molecular weight hydrocarbon or mixture of such halogenated hydrocarbons such as chlorinated petroleum wax, effecting the condensation in the presence of a Friedel-Crafts catalyst. This alkvlation may also be carried out by using high molecular weight unsaturated aliphatic hydrocarbons (such as eicosylene, cerotene, melene, polymerized isobutylene, etc.) or high molecular weight alcohols (such as myricyl alcohol, ceryl alcohol, 'etc.) using-Kasai or anhydrous aluminum chloride as a catalyst. The Friedel-Crafts synthesis is preferred because it affords a convenient means of controlling the degree of allgvlation," and as a source of the alkyl substituent preference is given to mixed high molecular weight hydrocarbons typified by those which characterize the heavier products of petroleum, such as heavy petroleum oils of the lubricant type, petrolatum and crystalline petroleum wax or other compounds which will result in relatively long chain aliphatic substituents. Special preference is given to petroleum wax of melting point not substantially less than about 120 R, which is predominantly L comprised of aliphatic hydrocarbons having a molecular weight of at least 350 and containing at least twenty carbon atoms.

Examples of hydroxyaromatic or oxyaromatic compounds which may be used in the alkylation reaction are: phenol, resorcinol, hydroquinone, catechol, cresol, xylenol, hydroxy-diphenyl, benzylphenol, phenyl-ethyl-phenol, phenol resins, methyl-hydroxydiphenyl, alpha and beta naphthol, xylyl naphthol, benzyl phenol, anthranol,

phenyl-methyl naphthol, phenanthrol, anisole, beta naphthyl methyl ether, chlorphenol and the like. Preference in general is to the monohydroxy phenols otherwise unsubstituted, par ticular preference being given to phenol and alpha and beta naphthol. Mixed alkyl-aryl and. aralkyl-aryl ethers such as anisole and betanaphthyl-methyl ether are given as examples because the Friedel-Crafts reaction with these ethers is accompanied by some rearrangement, yielding free hydroxyl groups.

The substitution of the alkyl acid residue for a nuclear hydrogen atom in the alkylated hydroxyaromatic compound or product may be effected (a) by condensation of the alkylated hydroxyaromatic compounds with unsaturated aliphatic acids such as oleic acid, using a socalled kationoid catalyst; (22) by condensation of the alkylated hydroxyaromatic compounds with halogenated aliphatic or cycle-aliphatic acids such as chloracetic, chlorstearic and chlornaphthenie acids with a Friedel-Crafts reaction, aluminum chloride being a preferred catalyst; and (c) by rearrangement of aryl ether aliphatic acids in the presence of kationoid catalysts such as I-ICl gas. The preferred procedure consists in condensing the unsaturated acids with the alkylated hydroxyaromatic compounds in the presence of anhydrous AlCls. Acids which may be used in this preferred procedure are typified by oleic, elaidic, maleic, acrylic, erucic, and sorbic acids. Procedure (0) above gives a wider latitude of aliphatic acid substituents to choose from; typical chlor-acids which may be used in this procedure being chloracetic acid, chlorbutyric acid, chlorcaprylic acid, chlorpalmitic acid, chlorstearic acid, etc.

The metal-phenate, metal-carboxylate salts derived from complex acids of the type obtained according to the foregoing general procedures may be prepared (a) by reacting the alkylated hydroxyaryl-aliphatic acid with an alcoholate of the desired metal in an amount equivalent to the combined hydroxyl and carboxyl content, (b)

by formation first of the alkylated hydroxyaromatic carboxylate salt, followed by reaction with an alcoholate of the desired metal to replace the hydroxyl hydrogen, and (c) by reaction of the alkyl-substituted hydroxyaryl-aliphatic acid with an alkali (sodium) alcoholate in an amount sufficient to neutralize both the hydroxyl and carbon] hydrogens, followed by double decomposition With an equivalent amount of analcoholsoluble anhydrous salt of the desired metal.

The metals contemplated herein may be broadly classified as metals of groups one to eight, inclusive, of the periodic system, which are capable of forming carboxylate salts. These metals comprise the following: the alkali metals: lithium, sodium, potassium, rubidium and caesium; the alkaline earth group: beryllium, magnesium, calcium, strontium and barium; the metals zinc, cadmium, mercury, scandium; the metals aluminum, gallium, indium, thallium, titanium, zirconium, cerium, thorium; germanium, tin and lead; vanadium, columbium and tantalum; arsenic, antimony and bismuth; chromium, molybdenum, tungsten and uranium; rhenium, manganese, iron, cobalt and nickel; ruthenium, rhodium and palladium; osmium, iridium and platinum.

Some of the rare earth metals are given in the foregoing. Other rare earth metals suitable for the formation of the phenate-carboxylate metal salts of hydroxyaromatic-aliphatic acids 'are those now commercially available as the cerium and yttrium group: namely, a mixture of praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thallium and lutecium.

As stated above, the Friedel-Crafts reaction for alkylating the hydroxyaromatic compound affords a convenient means of controlling the degree of alkylation of the product. accomplished by controlling: (a) the chlorination of the aliphatic hydrocarbon and (b) the reacting proportions of the chlorinated aliphatic hydrocarbon and the hydroxyaromatic compound used in the Friedel-Craits reaction. As is well known to those skilled in the art, the replacement of nuclear hydrogen in the hydroxyaromatic compound with an aliphatic group is, in the Friedel-Crafts synthesis, effected by reaction of such nuclear hydrogen with chlorine in the chlorinated aliphatic compound, the substitution being effected with evolution of HCl. It will thus be seen that the number of chlorine substituents in a chlorinated aliphatic compound corresponds to the number of valences (v in general Formula IV) which will be satisfied by or attached to hydroxyaromatic nuclei in the product of the reaction. For example, in a reaction where a quantity of pure monochlor-aliphatic hydrocarbon containing, say, three atomic proportions of chlorine is reacted with one molecular proportion of hydroxyaromatic compound, the resulting alyklated product, RV(T(OH)YIJ)11,, is one in which 1; and n are equal to 1 and there are three aliphatic groups R" attached to one nucleus '1". On the other hand, assuming a reaction in which a quantity of pure trichloraliphatic hydrocarbon containing 3 atomic proportions of chlorine is reacted with 1 molecular proportion of hydroxyaromatic compound, the;

product would be one in which 0 and n of general Formula IV are each equal to 3, and the solubilizing action of a single aliphatic group would be distributed among three nuclear hydroxyaromatic groups. It is due to this latter cation that we consider it preferable that the aliphatic hydrocarbon compounds.

This iS number of valence bonds 0" (in R of Formulae IV, etc.) be maintained within the range of from 1 to 4 hereinabove specified. In other words, it appears that the required oil-solubilizing and oil-improving action of the aliphatic substituent R particularly where the aliphatic substituent is a heavy alkyl group such as a wax derivative and the agent is to be used for multi- -functional activity in viscous oils, is not obtained R"(T(OM) (Z.COOM' Yb) n (Formula IV) in which 17 and n are greater than .4. Hence, for use in the Friedel-Crafts reaction the chlorinated high molecular weight aliphatic material should be a compound, or should be predominantly comprisedof compounds, in which the chlorine content is not greater than a tetrachlor compound.

As will be readily apparent to those skilled in the art, the chlorination of an aliphatic material such as a liquid petroleum fraction or a crystalline petroleum wax will normally or usually result in a mixture of monoand poly-chlor- Consequently, the product of a Friedel-Crafts reaction between such chlorinated material and a hydroxy-' aromatic compound will be a mixture of different compounds corresponding to different values of v and n in the formula R (T(OH)Yb)n, and the final alkylated metal-oxyaromatic aliphatic acid salt derived therefrom according to the reactions described above will likewise be a mixture of compounds corresponding to different values of n and v in general Formula IV. It will be understood, therefore, that the specific values for v and n in the above formula, as well as the formula itself, relate to the different specific compounds present in such a mixture which characterize it as a product of the present invention.

However, in the case of a pure compound corresponding to general Formula IV or in mixtures thereof, we have, as previously stated, discovered that for a satisfactory product, the ratio by weight of hydroxyaromatic component (T(OH) )n to the corresponding alkylated hydroxyaromatic nucleus or component (R (T(OH))n) should not be greater than a certain critical maximum ratio which varies with constituents, conditions of use, and properties desired, as discussed in detail hereinabove.

The above-mentioned ratio of hydroxyaromatic component to the corresponding alkylated hydroxyaromatic component (T(OH) in RV(T(OH) )11.

in which the hydroxyaromatic component is calculated as phenol and which is therefore herein referred to as the phenol content or phenolic ratio, is usually calculated from the weight of the hydroxyaromatic compound used up in the alkylation reaction and from the total weight of alkylated compound resulting from such alkylation reaction, as will be readily understood by those skilled in the art.

For example, when the Friedel-Crafts synthesis is used for alkylation, the aliphatic hydrocarbon mate'rial, is first chlorinated until the weight of chlorine, absorbed indicatesthat the average composition of the chlorinated product corresponds roughly (in the case of a high molecular weight aliphatic hydrocarbon) to, say, a dichlor-aliphatic hydrocarbon. Such a product will, of course, contain some monoand trichlor compounds and probably some tetrachlor compounds. The reacting proportions (based on atomic proportions of chlorine to one mol of hydroxyaromatic compound) are then selected so that the theoretical product of the Friedel- Crafts reaction will give the approximate phenolic ratio desired. After the Friedel-Crafts reaction and purification of the product the weight of aliphatic material in the chlorinated aliphatic starting material is subtracted from the weight of the alkylated or aliphatic-substituted product to obtain the weight of hydroxyaromatic material ((T(OH))n) actually combined or used up in the alkylation synthesis. From this value and the weight of the alkylated product (R (T(OI-I) )n) the phenolic ratio or phenol content can be readily calculated. If there are other substituents (Yb) on the hydroxyaromatic nucleus in addition to the monoor polyvalent aliphatic groups, a deduction should be made for them before calculating the phenolic ratio, an operation which will be apparent to those skilled in the art.

When it is desired to obtain a nitro or amino group as the substituent Yb in general Formula IV, the hydroxyaromatic compounds are alkylated and converted to the hydroxyaryl-aliphatic 1. ALKYLATION or PHnNoL A parafiln wax melting at approximately 120 F. and predominantly comprised of compounds having at least twenty carbon atoms in their molecules is melted and heated to about 200 F., after which chlorine is bubbled therethrough until the wax has absorbed from 16 per cent to 20 per cent of chlorine, such product having an average composition between a monochlor-wax and a dichlor-wax or corresponding roughly to a dichlor-wax. Preferably the chlorination is continued until about /6 the weight of the chlorwax formed is chlorine. A quantity of chlorwaxthus obtained, containing 3 atomic proportions of chlorine, is heated to a temperature varying from just above its melting point to not over 150 F., and 1 mol of phenol (CcHsOI-I) is admixed therewith. The mixture is heated to about 150 F., and a quantity of anhydrous aluminum chloride corresponding to about 3 per cent of the weight of the chlor-wax in the mixture is slowly added to the mixture with active stirring. The rate of addition of the aluminum chloride should be sufficiently slow to avoid violent foaming, and during such addition the temperature should be held at about 150 F. After the aluminum chloride has been added, the temperature of the mixture may be increased slowly (to control the evolution of 1101 gas) to a temperature of from 250 F. to 300 F.350 F. If the emission of HCl gas has not ceased when the final temperature is reached, the mixture may be held at 350 F. for a short time to allow completion of the reaction; but to avoid possible mea recracking of the wax the mixture should not be heated appreciably above 350' F., nor should it be held at that temperature for any extended length of time.

Removal of non-alkylated material (phenol) can be effected generally by water-washing, but itis preferable to treat the water-washed product with super-heated steam, thereby insuring complete removal of the unreacted material and accomplishing the drying of the product in the same operation.

The wax-substituted phenol thus obtained may be characterized by the general formula R (T(OH)Yb)n, in which R represents at least one aliphatic group or radical characteristic of paraffin wax having a valence v of from 1 to 4; T represents a monocyclic aromatic nucleus; Yb represents residual hydrogen, 1) being a number corresponding to the number of valences on. the nucleus T not satisfied by R and (OH) and n is a number from 1 to 4 corresponding to the valences v on the aliphatic group or groups R which are satisfied by the nuclear group or groups T(OH)Yb.

A wax-substituted phenol prepared according to the above procedure, in which a quantity of chlorwax containing 3 atomic proportions of chlorine (16 per cent chlorine in the chlorwax) is reacted with one mol of phenol, may, for

brevity herein, be designated as wax-phenol (3-l6). Parenthetical expressions of this type (AB) will be used hereinafter in connection with the alkylated hydroxyaromatic compounds to designate (A) the number of'atomic proportions of chlorine in chlor-aliphatic material reacted with one mol of hydroxyaromatic compound in the Friedel-Crafts reaction, and (B) the chlorine content of the chlor-aliphatic material. In the above example A==3 and. 3:16. This same designation will also apply to the metaloxyaromatic-aliphatic-metal carboxylate derivativea 2. Fomrarron or Wax-Sonsrrrornn HYnRoxYvnnNrL STEARIC ACID ((1) Condensation of unsaturated aliphatic acids with wax-phenol One molecular proportion of wax-phenol (3-16) prepared according to the foregoing procedure was admixed with one molecular proportion of oleic acid. The mixture was heated to a temperature of about 150 F. and one molecular proportion of AlCla was gradually added thereto with stirring to control the evolution of H01. After addition of the aluminum chloride the temperature of the reaction mixture was raised to about 250 F. and held at that temperature during a two-hour period-to complete the reaction.

The reaction mixture was then treated with. water and kept acid with hydrochloric acid to remove all traces of aluminum, being repeatedly washed until the aqueous extract did not contain Al(OI-I)3 when made ammoniacal, followed by washing with water until free of HCl. The operation of water-washing was facilitated by the use of a diluent such as benzol or Stoddard Solvent, the solvent thereafter being distilled, whereby any'entrained water was removed. The reaction product was then steam-treated with superheated steam at a temperature of about 200 C. to remove any unreacted aliphatic acid. The operation of steam-treating is facilitated by use of a stirrer, whereby better contacting with steam is obtained and run-back of condensed water is eliminated. Steam was passed through the mixture at about 200 C. until the distillate showed a negligible neutralization number, in-

dicating that any unreacted aliphatic acid was removed. When the steam-treat was finished, which generally requires about 10 hours, the steam vapors were removed by blowing with a non-oxidizing gas such as nitrogen, thereby yielding an anhydrous product, Wax-hydroxyphenyl-stearic acid, in which the stearic acid group was attached to the phenyl nucleus at an intermediate point on the chain.

By the use of a polycarboxylic acid such as maleic acid, at least dicar'boxylation results, forming hydroxyphenyl-succinic acid. By using wax-naphthol the corresponding wax-naphtholaliphatic acid is obtained.

(b)C'o nd'ensati0n of halogenated aliphatic acids with war-phenol In this procedure one mol of wax-phenol (3-16) was condensed with one mol of chlorstearic acid in the presence of onemol of AlClz following the same procedure for reaction and purification described above. The product here was wax-hydroxyphenyl-alpha-stearic' acid, since the condensation took place at the alpha carbon atom of the stearic acid group.

In both of the procedures (a) and (I?) described above the isolated or purified wax-hydroxyaromatic compound may be used. However, it is preferred to react the alkylated or wax-substituted phenol with the aliphatic acid without removing the aluminum or A1C13 therefrom following the Friedel-Crafts condensation.

FORMATION OF THE METAL SALTS Because of the tendency of alkali metal salts to emulsify, it is advantageousto prepare such salts in non-aqueous medium. The acid is treated with an alkali alcoholate (prepared from amyl or lower alcohol) or with a solution of alkali hydroxide in alcohol in an amount sufiicient to neutralize the hydroxyl and the carboxyl group. The reaction mixture is heated at about 300 F.

, may be prepared according to the foregoing procedure, after which it is reacted with an alcohol solution of cobaltous chloride having a cobalt content equivalent to the sodium in the original salt. The reaction mixture is heated to'a temperature of about 350 and held at that temperature for about 2 hours, during which time the alcohol distills 01f with completion of the reaction. The cobalt salt of the wax-hydroxyphenyl stearic acid thus formed is purified by settling and centrifuging or water-washing to remove reaction salts.

We have found that salts of the type contemplated herein in which the carboxyl group is in an aliphatic or cycloaliphatic substituent are superior to similar wax-aromatic acid salts in which the carboxyl group is attached to the nucleus in that the reaction salts 'formed in their synthesis may be more easily removed and further in that they have less tendency to emulsify.

Salts of wax-substituted hydroxyaromatic carboxylic acids can be prepared from other monoor poly-cyclic and monoor poly-hydric hydroxyaromatic compounds and other aliphatic or cycloaliphatic acids by following the general procedure described. Salts of wax-substituted naphthol-stearic acid, for example, represent another group of desirable oil-improving agents within the general class contemplated herein. Similar salts may also be obtained with other alkyl substituents than those'derived from petroleum wax, although, as indicated above, aliphatic hydrocarbons of the so-called petroleum wax or wax type (having at least 20 carbon atoms) are preferred because of the multifunctional activity of the resulting products.

To demonstrate the effectiveness of compounds or products of the type herein described as mineral oil-improving agents, we have conducted several comparative tests, the results of which are listed below, with representative mineral oils alone and with the same oils blended with typical improving agents of the type contemplated herein.

POUR POINT-DEPRESSION The metal salts of wax-substituted hydroxyaromatic aliphatic acids of the type contemplated herein, in which both the' hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal,

are, except in certain instances where the aryl.

nucleus carries another substituent such as a low alkyl group, effective pour point-depressants, as indicated by representative compounds in Table I below. The results in this table were obtained from blends of mineral lubricating oil having a Saybolt viscosity of 67 seconds at 210 F. and an A. S. T. M. pour test of +20 F.

Table I A. S. T.M. pour tests on oil blends containing Improving agent improving agents Deg. Deg. Deg. Deg. Oobaltous pheuate-cobaltous carboxylate salt of wax-hydroxyphenyl-steenc acid (346) +20 ,20 Vanadyl phenate-vanadyl carboxylate salt of wax-hydroxyphenyl-stearlc acid (3-14) +20 25 +10 Oobaltous phenate-cobaltous carboxylate salt of wax-naphthol-stearlc acld (314) -L -J +20 0 +20 Cobaltous phenate-cobsltous carboxylate salt of wax-cresolstearic acid (2l6). a +20 +25 Titanium phenate-titanium carboxylate salt of wax-hydroxyphenyl-steanc acid (3-14) .l +20 l0 +10 Stannous phenate-stannous carboxylate salt of wax-hydroxyphenyl-stearic 801d. (3-14) +20 +5 V. I. IMPROVEMENT As was previously pointed out, certain substituents such as low alkyls in the wax-substituted aryl nucleus tend to reduce materially the pour-depressing action of the improving agents herein without disturbing the property of these compounds to improve the viscosity index. The efiect on the pour-depressing action is indicated by the cresol derivative in the above table, and the effectiveness of these compounds to improve the viscosity index'is indicated in Table 11 below. The viscosity index (V. I.) data was obtained in the conventional manner from the Saybolt viscosity of the oil and the oil blends at 100 F. and

210 F. The oil used was a viscous mineral oil of the lubricant type.

per hour.

Table II Improving agent used Wt. cone. 100 210 V. I

' Per cent None 142.3 41.8 76. l Cobaltous phenate-cobaltous carboxylate salt of wax-hydroxyphenyl-stearic acid (3-16) 1 148.9 42.6 86.2 Vanadyl phenateanadyl carboxylate salt of wax-hydroxyphenylsteanc acid (3-14) 1 151.7 42.5 80.8 Cobaltous phenate-cobaltous carboxylate salt of wax-naphtha] stearic acid (3-14). 91. 9

one 78.3 Cobaltous phenate boxylate salt of wax-hydroxyphenyl-stearic acid (3-14) 1 153.3 43.1 92.4 Oobaltous phenate-cobaltous carboxylate salt of wax-cresol stearic acid (2-16) 1 163.3 43.1 92.4 Cobaltous phenate-cobaltous carboxylate salt of wax-xylenol alphastearic acid (2-18) 1 151.6 42.7 85.2 Cobaltous phenate-cobaltous carboxylate salt 01 wax-chlor-hydroxyphenyl-stearic acid (2-16) 1 [49.7 42.8 90 9 Cobaltous phenate-cobaltous carboxylate salt of wax-p-hydroxyphenyl-stearic acid (2-14) 1 155.2 42.9 84.5 Cobaltous phenate-cobaltous carboxylate salt of wax-amyl betanaphthol-stearic acid (3-18) 1 156.7 43.3 91.8 Titanium phenate-titanium carboxylate salt of wax-hydroxyphenyl-stearic acid (3-14) 1 152.2 42.8 86.8 Stannous phenate-stannous earboxylate salt of wax-hydroxyphenyl-stearic acid (314). 1 152.3 42.7 84.1

OPERATION TEST In addition to the foregoing tests we have also made tests on an oil and an oil blend containing a representative improving agent of the type contemplated herein to determine the comparative behavior of the unblended oil and the improved oil under actual operating conditions. The test was carried out in a single cylinder C. F. R. engine. The engine was operated continuously over a time interval of 28 hours, with the cooling medium held at a temperature of about 390 F., at a speed of 1200 R. P. M., which was equivalent to a road speed of about 25 miles The oil temperature was held at about 150 F. during the test.

The oil used in this testwas a lubricating oil stock of 120 seconds Saybolt viscosity at 210 F. and the conditions observed were: (a) the extent to which the piston rings were stuck, (b) the extent to which the slots inthe oil rings were filled with deposit, and (c) the amount of carbonaceous deposits in the oil. The Oil indicated as A in Table III below is the unblended oil; Oil B is the same 'oil containing A; per cent of the cobaltous phenate-cobaltous carboxylate salt of wax-hydroxyphenyl alpha-stearic acid (3-16) Oil C is another sample of unblended oil; and Oil Df is Oil C blended with A; per cent of the vanadyl phenate-vanadyl carboxylate salt of wax-hydroxyphenyl-stearic acid (3-14) Table III Ring condition Oil Degrees stuck g gi s ggg N. N.

From the foregoing results it will be apparent that phenate-carboxylate metal salts of alkylated hydroxyaromatic aliphatic acids of the type contemplated by this invention are efiective oilimproving agents and the preferred wax-substituted products are characterized by the fact that they have, through the presence of the wax-substituted aryl nucleus and the metal substituents, multifunctional activity. Although we do not wish to be bound in any regard by anytheory as to the function which the metal substituents have, it is believed that such substituents act by promoting the preferential oxidation of the alkylated hydroxyaromatic-aliphatic acid salt molecule, thereby taking up active oxygen and acting as a direct antioxidant; also by acting as a peptizing agent on any sludge that is formed in the oxidation of the oil; and in the event an alkali or alkaline earth metal is present as the metal substituent, the salts act by neutralizing strong acids in the oil, particularly sulfur acids such as may be formed by oxidation. The improved properties obtained and the degree of improvement in a particular property may be varied with the metal substituents, the aryl constituents, the degree of alkylation of the aryl nucleus, and the aliphatic acid residue.

As to the degree of alkylation, it is important that the aryl nucleus be sufilciently alkylated to provide a final product which is soluble" or miscible in the particular mineral oil fraction with which it is to be blended without tendency toward gelation-that is, one which will remain uniformly dispersed in the oil in sufficient amount to efiect the desired improvement under normal conditions of storage and use.

The amount of improving agent used may be varied, depending upon the mineral oil or the mineral oil fraction with which it is blended and the properties desired in the final oil composition. The alkylated hydroxyaromatic-aliphatic acid salts of the type described herein may be used in amounts ranging from one-sixteenth per cent to ten per cent, and in general compositions of the desired improvedproperties may be obtained with these improving agents in amounts of from one-sixteenth per cent to two per cent.

It is to be understood that while we have described certain preferred procedures which may be followed in the preparation of the alkylated hydroxyaromatic-aliphatic acid salts used as improving agents in the mineral oil compositions contemplated by this invention and have referred to various representative constituents in these improving agents, such procedures and examples have been used for illustrative purposes only. The invention, therefore, is not to be considered as limited by the specific examples given but includes within its scope such changes and modifications as fairly come within the spirit of the appended claims.

We claim:

1. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal and in which part of the hydrogen of the aromatic nucleus has been replaced with a mineral oil-solubilizlng substituent.

2. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an hydroxyaromatic aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal and in which part of the hydrogen of the aromatic nucleus has been substituted with predominantly aliphatic material, said last-mentioned substituent comprising a sufilclent proportion of said salt to render same miscible with said oil under normal conditions of handling and use.

3. An improved mineral oil composition comprising a mineral oil having admixed therewith in vminor proportion an oil-miscible metal salt of a hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal.

4. An improved mineralv oil composition comprising a mineraloil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal and in which the alkyl substituent is attached to the aromatic nucleus and is derived from an aliphatic hydrocarbon having at least twenty carbon atoms.

5. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal and in which the alkyl substituent is attached to the aromatic nucleus and is derived from petroleum wax.

6. An improved mineral ofl composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal, the alkyl substituent in saidsalt being a high molecular weight aliphatic hydrocarbon derivative and the aromatic nucleus being poly-substituted with said aliphatic derivative.

7. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydro- .gen and the carboxyl hydrogen are substituted with metal, the alkyl substituent in said salt being derived from an aliphatic hydrocarbon having at least twenty carbon atoms and the aromatic nucleus'being poly-substituted with said aliphatic derivative.

8. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt .of an alkyl-substituted hydroxyaromatic-aliphat carboxylic acid in which the hydroxyl hydrogen I and the carboxyl hydrogen are substituted with metal.

10. vAn improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt carboxyl hydrogen are substituted with metal and in which the alkyl substituent is derived from petroleum wax.

12. An improved mineral oil composition comprising a miner-a1 oil having admixed therewith a minor proportion of an oil-miscible salt of an alkyl-substituted naphthol-stearic acid in which the hydroxyl hydrbgen and the carboxyl hydrogen are substituted with metal and in which the alkyl substituent is derived from petroleum wax.

13. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted hydroxy-phenyl stearic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal and in which the alkyl substituent is derived from petroleum wax, the said phenyl nucleus being poly-substituted with said wax derivative.

14. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible salt of an alkyl-substituted naphthol-stearic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal and in which the alkyl substituent is derived from petroleum wax the said naphthol nucleus being poly-substituted with said wax derivative.

15. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a metal salt of an hydroxyaromatic condensation product comprising a hydroxyaromatic nucleus in which the hydroxyl hydrogen is replaced with metal and in which at least one nuclear hydrogen atom is substituted with an alkyl carboxylate radical selected from the group consisting of aliphatic and cyclo-aliphatic acid radicals wherein the carboxyl hydrogen is replaced with its equivalent weight of metal and in which at least .one other nuclear hydrogen atom is substituted with an aliphatic aromatic condensation product comprising a hydroxyaromatic nucleus in which the, hydroxyl hydrogen is replaced with metal and in which at least one nuclear hydrogen atom is substituted with an alkyl carboxylate radical selected from the group consisting of aliphatic and cycle-aliphatic acid radicals wherein the carboxyl hydrogen is replaced with its equivalent weight of metal and in which at least one other nuclear hydrogen atom is substituted with an aliphatic hydrocarbon radical derived from petroleum wax.

17. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a metal salt of an hydroxyaromatic condensation product comprising a hydroxyaromatic nucleus in which the hydroxyl hydrogen is replaced with metal and in which at least one nuclear hydrogen atom is substituted with an alkyl carboxylate radical selected from the group consisting of aliphatic and cyclo-aliphatic acid radicals wherein the carboxyl hydrogen is replaced with its equivalent weight of metal and in which at least one other nuclear hydrogen atom is substituted with an aliphatic hydrocarbon radical of at least twenty carbon atoms and at least one other hydrogen atom of the characterizing aromatic nucleus being substituted with a radical selected from the group consisting of hydroxyl, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and alkyl radicals containing less than twenty carbon atoms.

18. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a metal salt of an hydroxyaromatic condensation product comprising a hydroxyaromatic nucleus in which the hydroxyl 1 hydrogen is replaced with metal and in which at least one nuclear hydrogen atom is substituted with an alkyl carboxylate radical selected from the group consisting of aliphatic and cyclo-aliphatic acid radicals wherein the carboxyl hydrogen is replaced with its equivalent weight of metal and in which at least one other nuclear hydrogen atom is substituted with an aliphatic hydrocarbon radical derived from petroleum wax and at least one other hydrogen atom of the characterizing aromatic nucleus being substituted with a radical selected from the group consisting of hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and alkyl radicals containing less than twenty carbon atoms.

19. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of an oil-miscible metal salt of an alkyl-substituted hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal, said metal substituents being selected from metals of groups one to eight of the periodic system.

20. An improved mineral oil composition comprising a mineral oil having admixed therewith a minor proportion of a product of the type obtained by: chlorinating petroleum wax until about one-sixth of the reaction product is chlorine; reacting the chlorinated wax with a hy-. droxyaromatic compound in the proportion of one mol of the latter to an amount of the chlorinated wax containing from two to three atomic proportions of chlorine to form a wax-substituted hydroxyaromatic compound; substituting at least one nuclear hydrogen on the aromatic nucleus with an aliphatic acid group to form a wax-substituted hydroxyaromatic-aliphatic acid; and then substituting the hydroxyl hydrogen and the carboxyl hydrogen with metal.

21. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion, from about one-sixteenth to about ten' per cent, of an oilmiscible metal salt of an alkyl-substituted hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal.

22. An improved mineral oil composition comprising a viscous mineral oil fraction having admixed therewith a minor proportion from about one-sixteenth per cent to about ten per cent, of an oil-miscible metal salt of an alkyl-substituted hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with-metal, said allgvl substituent being derived from petroleum wax and attached to said hydroxyaromatic nucleus.

23. A composition of matter comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound having the general formula:

R (T(OM) (Z.COOM) Yb) n in which: T represents an aromatic nucleus; (OM) represents at least one hydroxyl group in which the hydroxyl hydrogen is replaced with its equivalent weight of a metal M, said group being attached to the nucleus T; (Z.COOM) represents an aliphatic acid residue in which Z is an alkyl radical attached to the nucleus T and selected from the group consisting of aliphatic and cyclo-aliphatic radicals, and COOM' is at least one carboxyl group attached to the alkyl radical Z, the carboxyl hydrogen thereof being replaced by a metal M; R represents at least one aliphatic group having a valence 2; of one to four and is attached by one valence bond only to at least one nucleus T; Yb represents'a monovalent radical selected from the group consisting of residual hydrogen, and hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals; b represents the number of Ybs and is equal to zero or a whole number corresponding to the valence bonds on the nucleus T not satisfied by R", (OM) or (Z.COOM) and n is a whole number from one to four; the substituent R, comprising a suflicient proportion of the metalorganic compound to render same miscible with said oil under normal conditions of handling and use.

24. A composition of matter comprising a mineral oil fraction and in admixture therewith a minor proportion of an oil-miscible metalorganic compound having the general formula:

R (T(OM) (Z.COOM' YbRc) n in which: T represents an aromatic nucleus; (OM) represents at least one hydroxyl group in which the hydroxyl hydrogen is replaced with its equivalent weight of metal M, said group being attached to the' nucleus T; (Z.COOM) represents an aliphatic acid residue wherein Z is an alkyl radical attached to the nucleus T and selected from the group consisting of aliphatic and cyclo-aliphatic radicals and COOM' represents at least one carboxyl group attached to the alkyl radical Z and wherein the carboxyl hydrogen is replaced with its equivalent weight of a metal M; R"' represents at least one polyvalent aliphatic hydrocarbon group of at least twenty carbon atoms having a valence v of from two to four; Yb represents a monovalent radical selected from the group consisting of residual hydrogen and chlorine, hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals; 1) represents the number of Yb"S and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied by R (OM), (COOM') and Re; Re represents monovalent aliphatic radicals; c represents the number of Rcs and is equal to zero or a whole number coresponding to the valences on the nucleus T not satisfied by R (OM), (COOM') and Yb; and n is a whole number from two to four.

25. An improving agent for mineral oils and the like comprising a metal salt of an al kyl-substituted hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal and in which the alkyl substituent contains at least twenty carbon atoms and is attached to the aromatic nucleus.

hit

areaare 26. An improving agent for mineral oils and the like comprising a metal salt of an hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal and in which at least the like comprising a metal salt of an hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal and in which at least one nuclear hydrogen atom of the aromatic nucleus is substituted with an aliphatic hydrocarhon group containing at least twenty carbon atoms, and at least one other nuclear hydrogen atom of the aromatic nucleus being substituted with a radical selected from the group consisting of hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals and aliphatic hydrocarbon radicals containing less than twenty carbon atoms.

28. An improving agent for mineral oils and the like comprising a metal salt of an hydroxyaromatic-aliphatic carboxylic acid in which the hydroxyl hydrogen and the carbonyl hydrogen are substituted with metal and in which at least one nuclear hydrogen atom of the aromatic nucleus is substituted with an aliphatic hydrocarbon group derived from petroleum wax.

29. An improving agent for mineral oils and the like comprising a metal salt of wax-substituted hydroxy-phenyl-stearic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal.

30. An improving agent for mineral oils and the like comprising a metal salt of wax-substituted naphthol-stearic acid in which the hydroxyl hydrogen and the carboxyl hydrogen are substituted with metal.

31. An improving agent for mineral oils and the like comprising a metalorganic compound having the general formula RW'I'TOM) (Z.COOM) Yb) 1:

in which: '1 represents an aromatic nucleus; (OM) represents at least one hydroxyl group attached to the nucleus '1, the hydroxyl hydrogen thereof being replaced with its equivalent weight of a metal M; (Z.COOM) represents an aliphatic acid residue in which Z is an alkyl radical attached to T and selected from the group consisting of aliphatic and cyclo-aliphatic hydrocarbon radicals, and 600M represents at least one carboxyl group with the hydrogen replaced by an equivalent weight of metal M and attached to the alkyl radical Z; R represents at least one aliphatic group having a valence v of one to four and is attached by one valence bond only to at least one nucleus '1; Yarepresents a monovalent radical selected from the group consisting of residual hydrogen and chlorine, hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals; 1) represents the number of YbS and is equal to zero or a whole number corresponding to the valence bonds on the nucleus T. not satisfied by R", (M) or (Z.COOM'); and n is a whole number from one to four; the substituent R comprising a sumcient proportion of the metalorganic compound to render same miscible with a mineral oil fraction under normal conditions of handling and use the like comprising a metalorganic compoimd having the general formula:

RWTKDM) (Z.COOM) YbRe) n in which: T represents an aromatic nucleus; (OM) represents at least one hydroxyl group in which the hydroiryl hydrogen is replaced with its equivalent weight of metal M, said group being attached to the nucleus T; (Z.COOM) represents an aliphatic acid residue wherein Z is an allryl radical attached to the nucleus T and selected from the group consisting of aliphatic and cycle-aliphatic radicals and 000M represents at least one carboxyl group attached to the alkyl radical Z and wherein the carboxyl hydrogen is replaced with its equivalent weight of a, metal M; R represents at least one polyvalent aliphatic hydrocarbon group of at least twenty carbon atoms having a valence v of from two to four; Yb represents a monovalent radical selected from the group consisting of residual hydrogen and chlorine, hydroxy, alkoxy, aroxy, aralkyl, aryl, alkaryl, halogen, nitro, amino and organic ester radicals; b represents the number of Yvs and is equal to zero or a whole number corresponding to the valences on the nucleus 1' not satisfied by R", (OM), (COOM) and Ref R0 represents monovalent aliphatic radicals; 0 represents the number of Res and is equal to zero or a whole number corresponding to the valences on the nucleus T not satisfied by R", (OM) (COOM) and Yb; and n is a whole number from two to four.

f a n P. o'r'ro.

32. An improving agent for mineral oils and 

